Transition metal oxide catalysts

ABSTRACT

A catalyst component comprising the product formed by heating at from 150*C. to 400*C., the secondary and/or tertiary alkoxide of the metals of Groups IVB, VB, and VIB, and, optionally, aluminum trialkyl, secondary aluminum alkoxide or tertiary aluminum alkoxide, the heating being done optionally in the presence of hydrocarbon solvent and/or tertiary alcohol and/or water; polymerization catalysts comprising (a) the catalyst component and (b) at least one alkyl or aryl of the metals of Groups IA, IIA, IIB, and IIIA; and a process for polymerization of ethylenically unsaturated olefins which utilizes the above polymerization catalyst.

United States Patent Jones [451 Aug. 29, 1972 [54] TRANSITION METALOXIDE CATALYSTS [72] Inventor: Richard Hamilton Jones, Newark,

Del.

[73] Assignee: E. I. du Pont de Nemours and Company, Wilmington, Del.

[22] Filed: March 20, 1970 [21] Appl. No.: 21,484

[58] Field of Search ..23/202; 252/461, 430, 463; 260/8078, 88.2, 94.9B, 94.9 D, 93.7, 429.5,

[56] References Cited UNITED STATES PATENTS 3,326,871 6/1967 Shepard eta1 ..260/94.9 2,912,421 11/1959 Juneland et al ..260/93.7 3,008,948 1 1/1961 Stampa et al ..260/94.9 3,297,414 1/ 1967 Magdiyasni et al..23/202 3,300,463 1/1967 Mare ..260/93.7 3,493,554 2/1970 Rekers..260/94.9 3,177,194 4/1965 Stampa ..260/94.9

FOREIGN PATENTS OR APPLICATIONS 853,229 11/ 1960 Great Britain 1,800,7428/1969 Germany OTHER PUBLICATIONS Cullinane et al., J. Appl. Chem., 1,Sept. 1951, pages 400- 406 Field et al., The Organic Chemistry ofTitanium, Butterworth, lnc., Wash, DC, 1965, pages 25- 34.

Primary ExaminerJoseph L. Schofer Assistant ExaminerEdward J. SmithAtt0rneyEarl L. l-landley [57] ABSTRACT A catalyst component comprisingthe product formed by heating at from 150C. to 400C, the secondaryand/or tertiary alkoxide of the metals of Groups IVB, VB, and VIB, and,optionally, aluminum trialkyl, secondary aluminum alkoxide or tertiaryaluminum alkoxide, the heating being done optionally in the presence ofhydrocarbon solvent and/or tertiary alcohol and/or water, polymerizationcatalysts comprising (a) the catalyst component and (b) at least onealkyl or aryl of the metals of Groups IA, 11A, 11B, and IRA; and aprocess for polymerization of ethylenically unsaturated olefins whichutilizes the above polymerization catalyst.

21 Claims, No Drawings TRANSITION METAL OXIDE CATALYSTS This inventionrelates to a catalyst component; particularly this invention relates toa catalyst component which is made by heating secondary and/or tertiaryalkoxides of the metals of Groups IVB, VB, and VIB and, optionally,aluminum trialkyl and/or secondary and/or tertiary aluminum alkoxidesoptionally in the presence of tertiary alcohol and/or water and/orhydrocarbon solvent. More particularly, this invention relates to apolymerization catalyst comprising (a) the catalyst component and (b) atleast one alkyl or aryl of the metals of Groups IA, BA, BB, and IIIA.Even more particularly, this invention relates to a process forpolymerizing ethylenically unsaturated olefins which utilizes the metaloxide catalyst.

Catalysts formed by mixing either the salts, freshly precipitated oxidesor hydroxides of the metals of Groups IVB, VB and VIB with aluminumtrialkyl are known (US. Pat. No. 3,257,332). The hydrolysis of Group lVBmetal alkoxide (US. Pat. No. 2,943,066) and aluminum alkoxide to formtheir oxides which are used in catalysts for olefin polymerization isalso known. However, more active noncorrosive catalysts which do nothave to be removed after polymerization have been sought for thepolymerization of olefins.

A catalyst component which is a precipitate compris ing metal oxide andwhich is formed by the thermal decomposition of the alkoxides of themetals of Groups IVB, VB, and VIB, and optionally aluminum trialkyl orsecondary or tertiary aluminum alkoxide when used with an alkyl or arylof the metals of Groups IA, IIA, HR, and IIIA fills the aboverequirement. The catalyst component comprises the product formed byheating at from 150C. to 400C. a substance comprising (a) 100-5 molpercent (expressed as the mols of the metals of Groups IVB, VB, and VIBrelative to the mols of aluminum, plus the mols of the metals of GroupsIVB, VB, and VIB present in the substance) of at least one memberselected from the class consisting of secondary alkoxides of the metalsof Groups IVB, VB, and VIB and tertiary-alkoxides of the metals of theGroups IVB, VB, and VIB, and (b) -95 mol percent (expressed as the molsof aluminum relative to the mols of the metals of Groups IVB, VB, andVIB plus the mols of aluminum present in the substance) of a memberselected from the class consisting of aluminum trialkyl, secondaryaluminum alkoxide, tertiary aluminum alkoxide and mixtures thereof.Throughout the specification and claims, Groups IA, IIA, lIB, IIIA, IVB,VB, and VIB refer to those groups in the Periodic Table of The Elements,depicted on pages 60-61 of the Handbook of Chemistry" by N. A. Lange,Revised th Edition, 1967 and substance is as is defined in sentence twoof this paragraph.

The heating of the substance normally is from 1 second to one hour with30 seconds to minutes usually being sufficient for the metal oxideprecipitate to form. The preferred temperature range for the heating isfrom 200 to 300C. Heating of the alkoxides of the metals of Groups IVB,VB, and VIB and the aluminum trialkyl or aluminum alkoxide is usuallydone in a hydrocarbon solvent, but can be done in the absence of one.Also, the heating can be done in the presence of water wherein the molratio of water to aluminum present is from 0. 1:1 to 2:1 with thepreferred amount of water present expressed as the mol ratio of water toaluminum being about 1: i.

If the secondary alkoxide of the Group lVB, VB, and

' VIB metals or the secondary aluminum alkoxide or aluminum trialkyl areutilized, it is beneficial to heat the substance in the presence oftertiary alcohol such that the tertiary alkoxides form before thesubstance is thermally decomposed into the oxides. The secondary ortertiary alkoxides of the aluminum of Group IVB, VB, and VIB metals foruse in the process for preparing the catalyst component as depictedabove, can be formed by heating the primary alkoxide with eithersecondary or tertiary alcohol. Other well known methods for productionof the secondary or tertiary alkoxides can also be utilized. Particulartertiary alcohols that are useful for the above purpose are t-butylalcohol, t-amyl alcohol, 2-methyl-2-pentanol, 2-methyl-2-hexanol, 2-methyI-Z-heptanol, and 4-methyl-4-heptanol. The amount of alcoholusually utilized is the amount necessary to convert the secondaryalkoxide of the Group IVB, VB, or VIB metals to tertiary alkoxides or toconvert the aluminum trialkyl or secondary aluminum alkoxides totertiary alkoxides, although an excess can be employed.

The preferred composition of the substance which is to be heated to formthe catalyst component comprises -50 percent (expressed as the mols ofthe metals of Groups IVB, VB, and VIB relative to the mols of the metalsof Groups IVB, VB, and VIB plus the mols of aluminum present in thesubstance) of at least one member selected from the class consisting ofsecondary alkoxides of the metals of Groups IVB, VB, and VIB andtertiary alkoxides of the metals of Groups IVB, VB and VIB and 15-50percent (expressed as the mols of aluminum relative to the mols'of themetal of Groups IVB, VB, and VIB plus the mols of aluminum present inthe substance) of a member selected from the class consisting ofaluminum trialkyl, secondary aluminum alkoxide, tertiary aluminumalkoxide and mixtures thereof. The normally employed secondary alkoxidesof the metals of Groups IVB, VB, and WE are tetraisopropyl titanate andtetraisopropyl zirconate, while the generally utilized tertiaryalkoxides of the metals of Groups IVB, VB, and VIB are tetra-t-butyltitanate, tetra-t-butyl zirconate, tri-t-butyl vanadate, tetra-t-amyltitanate, tetra-t-amyl zirconate and tri-tamyl vanadate. The normallyutilized aluminum trialkyls are triisobutyl aluminum and triethylaluminum while the generally used secondary aluminum alkoxide isaluminum isopropoxide and the usually employed tertiary aluminumalkoxides are aluminum-t-butoxide and aluminum-t-pentoxide.

Hydrocarbon solvents which are generally utilized are hexane,cyclohexane, n-hexadecane, benzene, toluene, xylene and chlorinatedaromatic hydrocarbon solvents.

The catalyst component is useful as a part of a polymerization catalystutilized in polymerizing olefins. Such a polymerization catalystcomprises (a) catalyst component as described above and (b) at least onemember selected from the class consisting of alkyls of the metals ofGroups IA, 11A, 11B, and IIIA and aryls of the metals of Groups IA, lIA,HE, and 111A. The amount of the alkyls and/or aryls of the metals ofGroups IA, 11A, 11B, and IIIA is normally 0.1:1 to 10:1, expressed asthe mol ratio of the metals of Groups IA, IIA, HE, and IIIA to the GroupIVB, VB and VIB metals, the preferred range is 0.1:1 to 1:1. The alkylswill normally contain one to 12 carbon atoms while the aryls willnormally contain six to 12 carbon atoms in each substituent alkyl oraryl. The preferred alkyls and aryls of the metals of Groups IA, IIA,11B, and IIIA are aluminum trialkyl, i.e., triisobutyl aluminum andtriethyl aluminum, magnesium dialkyl, i.e., diethyl magnesium, lithiumalkyl, i.e., n-butyl lithium, diphenyl magnesium and diethyl zinc withthe most preferred being triisobutyl aluminum and triethyl aluminum.

The polymerization catalyst is useful in the polymerization of olefinssince it is active, noncorrosive and generally does not have to beremoved after polymerization from the polymer, because it is normallywhite. A process for such is a process for the polymerization ofethylenically unsaturated olefins which comprises contacting said olefinat to 300C. with a catalytic amount of the polymerization catalyst setforth above. The process is usually run at from 0 to 30,000 psig. for0.1 to 1000 minutes, with the preferred pressures and times being 15 to2000 psig and 1 to 60 minutes, respectively. The preferred reactiontemperature is 25 to 250C. The amount of polymerization catalyst recitedabove in the reactor, is normally 0.001 to 2 percent by weight of thetotal weight of the contents of the reactor with 0.01 to 0.2 percentusually being sufficient. The olefin can be contacted with thepolymerization catalyst as a combination of the catalyst component andthe alkyls and/or aryls of the metals of Groups IA, 11A, 11B, and IIIAor the olefin can be contacted with the catalyst component first andthen the alkyls and/or aryls of the metals of Groups IA, IIA, IIB, and111A added or the olefin can be contacted with the catalyst component atthe same time as the alkyls and/or aryls of the metals of Groups IA,IIA, HE, and 111A.

The ethylenically unsaturated olefins which can be polymerized by theabove process include ethylene, propylene, mixtures of ethylene andl-olefins of more than two carbon atoms, mixtures of propylene andlolefins of more than three carbon atoms, mixtures of ethylene,l-olefins of more than two carbon atoms and diolefins, and mixtures ofpropylene, l-olefins of more than three carbon atoms and diolefins.Particularly useful l-olefins other than ethylene and propylene are 1-butene, l-pentene and l-octene, while particularly useful diolefins are1,4-hexadiene and dicyclopentadiene. The mol percent of the ethylenepolymerized as a mixture with propylene is usually 30 to 70 percent withthe mol percent of propylene being 70 to 30 although compositions goingto 100 percent of either component are useful. When the ethylene orpropylene is in combination with other l-olefins, the mol percent of theother l-olefin is usually from 0.1 to 30 percent with l to 10 percentbeing preferred. The mixtures which also contain diolefin usuallycontain up to 10 mol percent diolefin with 1 to 5 mol percent beingpreferred.

The polymers produced by the above process have uses which are wellknown, i.e., packaging films, tubing, etc.

The following examples are presented to illustrate but not to limit theinvention.

EXAMPLE 1 Into a 500-milliliter, three-necked flask blanketed withnitrogen were placed 200 milliliters of n-hexadecane, 3 milliliters(0.01

I titanate, and 20 milliliters t-butyl alcohol. The amount oftriisobutyl aluminum listed in Table I was then added. The mixture wasthen heated to remove excess isopropyl and t-butyl alcohol. Furtherheating to approximately 250C. caused the decomposition of the aluminumand titanium t-butoxides into aluminum and titanium oxides (theprecipitation temperature for each run is shown in Table 1). Heating at250C. under a slow stream of nitrogen was continued for 30 minutes toensure that all traces of alcohol formed during the alkoxidedecomposition were removed. Then the metal oxide slurry was cooled to50C. and ethylene at atmospheric pressure was passed through thereaction flask. Polymerization was initiated by adding 2.0 millilitersof 1.0 M triisobutyl aluminum. Polymerization was allowed to proceed for30 minutes at 50C. and was then terminated by adding 50 milliliters ofn-butyl alcohol. The product was thoroughly washed with a 50/50cyclohexane/acetone mixture and dried in a vacuum oven at C. Rates ofpolymerization were calculated as grams of polymer/gram catalyst/hourand are shown in Table I for each run.

Into a 500-milliliter, three-necked flask blanketed with nitrogen wereplaced 200 milliliters of n-hexadecane and 2.6 milliliters (6.0millimols) tetra-t-amyl titanate; the amount of aluminum t-butoxideindicated in Table II was also added for each run. The mixtures wereheated until precipitation occurred (normally about 250 C.) and heatingunder nitrogen flow was continued at 250 C. for 15 minutes afterprecipitation to remove alcoholic decomposition products. Then the metaloxide slurries were cooled to C. and ethylene at atmospheric pressurewas passed through the reaction flask. Polymerization was initiated byadding 1.0 milliliter of 1.0 M triisobutyl aluminum.

Polymerization was allowed to proceed for 15 minutes at 150C. and wasthen terminated by adding 50 milliliters of n-butyl alcohol. The productwas washed with 50/50 cyclohexane/acetone mixture and dried in a vacuumoven at 70C. The amount of polymerization product and polymerizationrates are given for each run in Table II.

TABLE II Rate of mol) tetraisopropyl Me] of Aluminum Grams of t-butoxidePolymerization Polymerization (g. of polymer/ g. of catalyst] Into aSOD-milliliter, three-necked flask blanketed with nitrogen were placed200 milliliters dry n-hexadecane, 1.8 milliliters (0.006 mol)tetraisopropyl titanate, 20 milliliters t-amyl alcohol and 0.003 mol oftriisobutyl aluminum. The mixture was heated to distill off isopropylalcohol and excess t-amyl alcohol and heating was continued to 250 C.under nitrogen flow for 30 minutes to remove t-arnyl alcohol formedduring alkoxide decomposition. The catalyst slurry was then cooled to 50C. and ethylene at atmospheric pressure was introduced. Polymerizationwas initiated by adding the amount of triisobutyl aluminum listed inTable III for each run. Polymerization was allowed to proceed for 30minutes at 50 C. and was then terminated by adding 50 milliliters ofn-butyl alcohol. The product was thoroughly washed with 50/50cyclohexane/acetone and dried in a vacuum oven at 70 C. Table IIIindicates the grams of product for each run and the rate ofpolymerization for each run.

TABLE 111 Rate of Polymerization (g. of polymer/ g. of catalyst/ MOI oftriiso butyl aluminum Grams of Used to Initiate Polymerization RunPolymerization Product hour) I 0.0005 10.1 30.1 2 0.00] l 1.6 34.8 30.002 6.7 I93 4 0.005 6.3 l8.0 5 0.010 7.6 22.2

EXAMPLE 4 isopropyl alcohol and convert the titanium isopropoxide to thetitanium alkoxide of the added alcohol and to finally remove excessalcohol and thoroughly decompose the tertiary alkoxides into titaniumand aluminum oxides. Heating was continued at 250 C. for 30 minutesunder a stream of nitrogen to remove alcoholate decomposition products.The oxide slurry was cooled to 50 C. and saturated with ethylene atatmospheric pressure. Polymerization was initiated by adding 0.001 molof triisobutyl aluminum. After polymerizing for 30 minutes at 50 C., thepolymerization was terminated by adding 50 milliliters of n-butylalcohol. The polymerization product was thoroughly washed with a 50/50solution of cyclohexane/acetone and dried in a vacuum oven at 70 C.Table IV, besides depicting the alcohol used, presents the temperatureat which precipitation of the oxides occurred, grams of product formedand rate of polymerization.

TABLE IV Rate of Tempera- Grams of Polymerization ture of Polymer- (g.of polymer] Alcohol Used to Precipiization g. of catalyst/ Run Make theAlkoxides tation Product hour) 1 Z-methyl-Z-butanol 230 C. 4.0 12 2Z-methyl-Z-pentanol 230 C. 6.3 18 3 2-mcthyl-2-hexanol 210 C. 12.9 39 4Z-methyI-Z-heptanol 228 C. 13.3 40 5 4-methyl-4-heptanol 210 C. 12.6 3 8EXAMPLE 5 Run 1 of Example 1 was repeated except that no tbutyl alcoholwas added to convert the tetraisopropyl titanate to titanium t-butoxide.Thermal decomposition was more difficult than with tertiary alkoxidesand decomposition to a gray-green solid occurred only after heating at279 C. for 5 minutes. When activated with 0.002 mol of triisobutylaluminum, polymerization of ethylene at atmospheric pressure and 50 C.was slow. Total product recovered was 1.5 grams which corresponds to apolymerization rate of 1.7 grams of product/grams of catalyst/hour.

EXAMPLE 6 In a SOD-milliliter flask were mixed 200 milliliters of dryn-hexadecane, 0.010 mol of the metal alcoholates listed in Table V, 20milliliters of t-butyl alcohol and 0.010 mol of triisobutyl aluminum.The mixture was heated to distill ofl" excess alcohols and to form themetal t-butoxide. Further heating was carried out to decompose thet-butoxides into oxides. Heating was continued at 275-280 C. for 30minutes under a flow of nitrogen to remove alcoholic decompositionproducts. The mixture was then cooled to 50 C. and ethylene atatmospheric pressure passed through. The catalyst was activated byadding 0.002 mol to triisobutyl aluminum and polymerization was allowedto proceed for 30 minutes. Then the reaction was terminated by adding 10milliliters of n-butyl alcohol. The product was thoroughly washed with a50/50 solution of cyclohexane/acetone and dried. Table V depicts theprecipitation temperatures for the oxides, the yield of polymerizationproduct in grams, and the rate of EXAMPLE7 Into a 500-milliliter,three-necked flask in a dry nitrogen atmosphere were added 200milliliters of dry n-hexadecane, 2.6 milliliters (0.006 mol)tetra-t-amyl titanate and the amount of triethyl aluminum listed inTable VI. The mixture was heated to precipitate the titanium in aluminumoxides. The resulting catalyst was white in Runs 1 through 4 and dark inRuns 5 and 6. Heating was continued at 250 C. under a stream of nitrogenfor minutes to remove any residual t-amyl alcohol formed during thermaldecomposition. The catalyst slurry was then cooled to 50 C. andsaturated with ethylene in atmospheric pressure. With excess ethylenepassing through the flask, polymerization was initiated by adding 0.001mol triisobutyl aluminum. Polymerization was allowed to proceed for 15minutes at 50 C. and was then terminated by adding n-butyl alcohol. Theproducts were thoroughly washed with a 50/50 solution ofcyclohexane/acetone and dried in a vacuum oven. Table VI depicts theamounts of triethyl aluminum added, the precipitation temperatures forthe oxides, the polymerization product yield in grams Into a500-milliliter, three-necked flask under a nitrogen flow of 900 cc. perminute were placed 200 milliliters of dry n-hexadecane and 2.3milliliters (0.006 mol) tetra-t-butyl titanate. As indicated in TableVII, either 0.003 or 0.006 mol of triethyl aluminum were added at atemperature of 120 C. The extent of titanate reduction was followed bymeasuring the ethane produced using the infrared band at 3.4 microns.The amount of ethane being evolved was continuously plotted on arecorder attached to the infrared instrument. It was assumed that 1 molof ethylene was being produced for each mol of ethane observed. When thedesired reduction of titanate had been achieved as indicated by theethane produced, the reduction was terminated by adding thestoichiometric amount of tbutyl alcohol to react with the residualtriethyl aluminum. Then the solution was heated to 247267 C. to inducethe precipitation of the metal oxides. Heating at 250 C. was continuedfor 15 minutes under nitrogen flow to remove alcohol as decompositionproducts. The catalyst slurry was cooled to 50 C. and the nitrogen flowreplaced by ethylene. Polymerization was initiated by adding 0.001 molof triisobutyl aluminum and was terminated after 15 minutes at 50 C. byadding n-butyl alcohol. The polymer was thoroughly washed with a 50/50solution of cyclohexane/acetone and dried in a vacuum oven at 30 C.Table VII presents the amount of triethyl aluminum added to thereaction, the valence of the titanium after reduction, the amount oft-butyl alcohol added to stop the reduction of the titanium, theprecipitation temperature of the metal oxides, yield of Into a500-mi1liliter, three-necked flask blanketed with nitrogen, were placed200 milliliters n-hexadecane, 2.3 milliliters (0.006 mol) tetra-t-butyltitanate, and 0.003 mol aluminum t-butoxide. With vigorous stirring, 3.0milliliters of 1.0 M water in t-butyl alcohol were added. The mixturewas heated and rapidly precipitated the mixed oxides at 238 C. Theheating was then continued at 250 C. for 15 minutes. The mixture wascooled to 50 C. and saturated with ethylene. Polymerization was startedby adding 0.001 mol of triisobutyl aluminum. After polymerizing for 15minutes, the reaction was terminated by adding 50 milliliters of n-butylalcohol. The product was washed thoroughly in a 50 percentcyclohexane/SO percent acetone mixture and was dried at 70 C. in avacuum oven. The dried polymer weighted 9.2 grams which corresponds tothe polymerization rate of 54 grams of polymer/ grams of catalyst/hour.

EXAMPLE 10 A comparative Example between catalyst with the heating stepand catalyst without the heating step. Catalyst without the heating stepInto a 500-milliliter, three-necked flask blanketed with nitrogen wereplaced 200 milliliters of dry decahydronaphthalene. The solvent washeated to 50 C. and the nitrogen was replaced with ethylene. Thefollowing catalyst components were then added: 10 millimols oftetraisopropyl titanate and 20 millimols of triethyl aluminum. Thepolymerization was attempted for 30 minutes at 50 C. and then terminatedwith 100 milliliters of n-butyl alcohol. No polymer was obtained.Catalyst with the heating step In a 500-milliliter, three-necked flaskblanketed with nitrogen were placed 200 milliliters of dry n-hexat 50 C.and was then terminated with 50 milliliters of n-butyl alcohol. Theresulting polymer was collected, washed and dried. Ten grams of polymerwere obtained.

Into a 500-milliliter, three-necked flask blanketed with nitrogen wereplaced 200 milliliters of n-hexadecane, l millimols of tetra-t-butyltitanate and 7 millimols of triethyl aluminum. The mixture was heated at250C. for 30 minutes to precipitate the titanium and aluminum oxide todrive off decomposition products produced during the formation of themixed oxides. Precipitation of the oxides occurred at 248C. The mixturewas then cooled to 50C. and saturated with ethylene. Polymerization wasinitiated by adding 2 millimols of triisobutyl aluminum. With excessethylene continually passing through the flask, polymerization wasallowed to proceed for 30 minutes at 50C. It was then terminated with 50milliliters of n-butyl alcohol. After washing and drying in a vacuumoven, the product weighed 19.6 grams.

EXAMPLE 1 l A reaction product of titanium and aluminum t-pentoxide wasprepared by mixing at 50C., 6.85 grams (0.034 mol) of aluminumisopropoxide, 20 ml. (0.067 mol) of tetraisopropyl titanate, and 20 ml.of t-arnyl alcohol with 0.60 ml. (0.033 mol) of water dissolved in 20ml. of t-amyl alcohol. The mixture was heated to 105C under nitrogenflow to remove isopropyl alcohol and excess t-amyl alcohol. The producthad a density of 0.945 g./cc.

Three ml. of the above product (which contained 0.006 g. atoms oftitanium and 0.003 g. atoms of aluminum) was added to 200 ml. of dryn-hexadecane in a 500 ml., three-necked flask blanketed with a nitrogenflow. The mixture was heated to precipitate the oxides and heating wascontinued at 250C for minutes under nitrogen flow to remove alcoholicby-products of the oxides formation. The mixture was cooled to 50C. andthe nitrogen flow was replaced with an ethylene flow at atmosphericpressure. Polymerization of ethylene was initiated by adding 0.001 molof n-butyl lithium. The polymerization was allowed to proceed for 15minutes at 50C with excess ethylene passing through the reactionmixture. The product was washed several times with a 50/50 mixture ofcyclohexane and acetone. After drying, the solid product weighted 1.3grams.

EXAMPLE 12 Two-hundred ml. of dry n-hexadecane were placed in a 500 ml.,three-necked flask blanketed with nitrogen and 0.006 mol of tetra-t-amyltitanate and 0.004 mol of triethyl aluminum were added. The mixture washeated to precipitate the oxides. Heating was continued for 15 minutesat 250C under nitrogen flow to remove any alcoholic products formedduring oxide formation. The mixture was cooled to 50C and the nitrogenflow replaced with ethylene. Polymerization was initiated by adding0.001 mol of diethyl zinc. Polymerization was allowed to proceed for 15minutes at 50C under excess ethylene flow at atmospheric pressure. Asmall amount of polymer of very high molecular weight was obtained.

EXAMPLE 13 In a 500 ml., three-necked flask blanketed with a nitrogenflow were placed 200 ml. dry n-hexadecane, 0.006 mol tetra-t-amyltitanate and 0.004 mol of diethyl aluminum hydride. The mixture washeated and solids precipitated at 243C. Alcoholic by-products of theoxide formation were removed by continuing to heat at 250C for 15minutes under nitrogen flow. The mixture was cooled to 50C and thenitrogen flow was replaced by an ethylene flow. Polymerization was theninitiated by adding 5.5 ml. of a solution prepared by mixing 0.0005 molof diphenyl magnesium and 0.0005 mol of triisobutyl aluminum. Thepolymerization was allowed to proceed for 15 minutes at 5 0C underexcess ethylene flow at atmospheric pressure. After drying, the productweighed 5.4 grams.

I claim:

1. A polymerization catalyst comprising (a) a catalyst componentcomprising metal oxide formed by heating in a solvent selected from theclass consisting of hydrocarbon solvent and chlorinated aromatichydrocarbon solvent at from 150C. to 400C. a substance consistingessentially of (l) 100 to 5 mol percent (expressed as the mols of themetals of Group IVB, VB, and VIB relative to the mols of aluminum plusthe mols of the metals of Groups IVB, VB, and VIB present in thesubstance) of at least one member selected from the class consisting ofsecondary alkoxides of the metals of Groups IVB, VB, and VIB andtertiary alkoxides of the metals of Groups IVB, VB, and VIB and (2) 0 tomol percent (expressed as the mols of aluminum relative to the mols ofGroups IVB, VB, and VIB plus the mols of aluminum present in thesubstance) of a member selected from the class consisting of aluminumtrialkyl, secondary aluminum alkoxides, tertiary aluminum alkoxides, andmixtures thereof, and (b) at least one member of the class consisting ofalkyls of the metals of Groups IA, IIA, 11B, and IIIA and aryls of themetals of Groups IA, 11A, 11B, and IIIA wherein the amount of (b)present is 0.01:1 to 10:1, expressed as the mol ratio of the metals ofGroups IA, IIA, I18, and IIIA to the Group IVB, VB, and VIB metals.

2. The catalyst of claim 1 in which the catalyst component is formed byheating the substance for 1 second to 1 hour.

3. The catalyst of claim 1 wherein the catalyst component is formed byheating the substance in the presence of tertiary alcohol.

4. The catalyst of claim 3 wherein the catalyst component is formed byheating the substance wherein aluminum is present in the presence ofwater such that the mol ratio of water to aluminum present is from 0. l:1 to 2:1.

5. The catalyst of claim 3 in which the tertiary alcohol is selectedfrom the class consisting of t-butyl alcohol, t-amyl alcohol,2-methyl-2-pentanol, 2-methyl- 2-hexanol, 2-methyl-2-heptanol and4-methyl-4-heptanol.

6. The catalyst of claim 1 in which the secondary alkoxides of themetals of Groups IVB, VB, and WE of the catalyst component are selectedfrom the class consisting of tetraisopropyl titanate and tetraisopropylzirconate and the tertiary alkoxides of the metals of Groups IVB, VB,and VIB of the catalyst component are selected from the class consistingof tetra-t-butyl titanate, tetraet-butyl zirconate, tri-t-butylvanadate, tetra-t-amyl titanate, tetra-t-amyl zirconate, and tri-tamylvanadate.

7. The catalyst of claim 6 in which the aluminum trialkyl of thecatalyst component is selected from the class consisting of triisobutylaluminum and triethyl aluminum, the secondary aluminum alkoxide isaluminum isopropoxide and the tertiary aluminum alkoxide of the catalystcomponent is selected from the class consisting of a1uminum-t-butoxideand aluminumtpentoxide.

8. The catalyst of claim 7 in which the catalyst component is formed byheating the substance at 200 to 300C. for 30 seconds to minutes whereinthe mol percent of 1) (expressed as the mols of the metals of GroupsIVB, VB, and VIB relative to the mols of the metals of Groups IVB, VB,and VIB plus the mols of aluminum present in the substance) is 85 to 50percent and the mol percent of (2) (expressed as the mols of aluminumrelative to the mols of metals of Groups IVB, VB and VIB plus mols ofaluminum present in the substance) is l5 to 30 percent.

9. The catalyst of claim 1 in which the hydrocarbon solvent is selectedfrom the class consisting of hexane, cyclohexane, n-hexadecane, benzene,toluene and xylene.

10. The catalyst of claim 1 in which the tertiary alkoxides of themetals of Groups IVB, VB, and VIB of the catalyst component are formedby heating primary alkoxides of the metals of Groups IVB, VB, and VIBwith a tertiary alcohol.

11. The catalyst of claim 8 wherein the alkyl of the metals of GroupsIA, IIA, IIB, and IIIA is selected from the class consisting oftriisobutyl aluminum, triethyl aluminum, diethyl magnesium, n-butyllithium and diethyl zinc and the aryl of the metals of Groups IA, IIA,I18, and IIIA is diphenyl magnesium.

12. The catalyst of claim 1 1 wherein (b) is an alkyl of the metals ofGroups IA, 11A, 1113, and IIIA and is selected from the class consistingof triisobutyl aluminum and triethyl aluminum.

13. A process for the polymerization of ethylenically unsaturated olefinwhich comprises contacting said olefin at from 0 to 300C. with acatalytic amount of the catalyst of claim 1.

14. The process of claim 13 wherein the pressure and time ofpolymerization are from 0 to 30,000 psig. and 0.1 to 1000 minutes,respectively.

15. The process of claim 13 wherein said olefin is selected from theclass consisting of ethylene, propylene, mixtures of ethylene andl-olefins of more than two carbon atoms, mixtures of propylene andlolefins of more than three carbon atoms, mixtures of ethylene,l-olefins of more than two carbon atoms and diolefins, and mixtures ofpropylene, l-olefins of more than 3 carbon atoms and diolefins.

16. A process for the polymerization of ethylenically unsaturated olefinwhich comprises contacting said olefin at from 0 to 300C. with acatalytic amount of the catalyst of claim 3.

17. A process for the polymerization of ethylenically unsaturated olefinwhich comprises contacting said olefin at from 0' to 300C. with acatalytic amount of talyst of cla m 6.

A process or the polymerization of ethylenically unsaturated olefinwhich comprises contacting said olefin at from 0C. to 300C. with acatalytic amount of the catalyst of claim 7.

19. A process for the polymerization of ethylenically unsaturated olefinwhich comprises contacting said olefin at from 0C. to 300C. with acatalytic amount of the catalyst of claim 8.

20. The process for the polymerization of ethylenically unsaturatedolefin which comprises contacting said olefin at from 0C. to 300C. witha catalytic amount of the catalyst of claim 1 1.

21. The process for the polymerization of ethylenically unsaturatedolefin which comprises contacting said olefin at from 0C. to 300C. witha catalytic amount of the catalyst of claim 12.

2 3 I UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 37,9 Dated August 29, 1972 In'vent RICHARD HAMILTON JONES It is certifiedthat error appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

001. 11, Claim 8, last line should read is 15 t 5 percent.

Signed and sealed this 20th day of February 1973.,

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCI LALK Attesting Officer Commissionerof Patents

2. The catalyst of claim 1 in which the catalyst component is formed byheating the substance for 1 second to 1 hour.
 3. The catalyst of claim 1wherein the catalyst component is formed by heating the substance in thepresence of tertiary alcohol.
 4. The catalyst of claim 3 wherein thecatalyst component is formed by heating the substance wherein aluminumis present in the presence of water such that the mol ratio of water toaluminum present is from 0.1:1 to 2:1.
 5. The catalyst of claim 3 inwhich the tertiary alcohol is selected from the class consisting oft-butyl alcohol, t-amyl alcohol, 2-methyl-2-pentanol,2-methyl-2-hexanol, 2-methyl-2-heptanol and 4-methyl-4-heptanol.
 6. Thecatalyst of claim 1 in which the secondary alkoxides of the metals ofGroups IVB, VB, and VIB of the catalyst component are selected from theclass consisting of tetraisopropyl titanate and tetraisopropyl zirconateand the tertiary alkoxides of the metals of Groups IVB, VB, and VIB ofthe catalyst component are selected from the class consisting oftetra-t-butyl titanate, tetra-t-butyl zirconate, tri-t-butyl vanadate,tetra-t-amyl titanate, tetra-t-amyl zirconate, and tri-t-amyl vanadate.7. The catalyst of claim 6 in which the aluminum trialkyl of thecatalyst component is selected from the class consisting of triisobutylaluminum and triethyl aluminum, the secondary aluminum alkoxide isaluminum isopropoxide and the tertiary aluminum alkoxide of the catalystcomponent is selected from the class consisting of aluminum-t-butoxideand aluminum-t-pentoxide.
 8. The catalyst of claim 7 in which thecatalyst component is formed by heating the substance at 200* to 300*C.for 30 seconds to 15 minutes wherein the mol percent of (1) (expressedas the mols of the metals of Groups IVB, VB, and VIB relative to themols of the metals of Groups IVB, VB, and VIB plus the mols of aluminumpresent in the substance) is 85 to 50 percent and the mol percent of (2)(expressed as the mols of aluminum relative to the mols of metals ofGroups IVB, VB and VIB plus mols of aluminum present in the substance)is 15 to 30 percent.
 9. The catalyst of claim 1 in which the hydrocarbonsolvent is selected from the class consisting of hexane, cyclohexane,n-hexadecane, benzene, toluene and xylene.
 10. The catalyst of claim 1in which the tertiary alkoxides of the metals of Groups IVB, VB, and VIBof the catalyst component are formed by heating primary alkoxides of themetals of Groups IVB, VB, and VIB with a tertiary alcohol.
 11. Thecatalyst of claim 8 wherein the alkyl of the metals of Groups IA, IIA,IIB, and IIIA is selected from the class consisting of triisobutylaluminum, triethyl aluminum, diethyl magnesium, n-butyl lithium anddiethyl zinc and the aryl of the metals of Groups IA, IIA, IIB, and IIIAis diphenyl magnesium.
 12. The catalyst of claim 11 wherein (b) is analkyl of the metals of Groups IA, IIA, IIB, and IIIA and is selectedfrom the class consisting of triisobutyl aluminum and triethyl aluminum.13. A process for the polymerization of ethylenically unsaturated olefinwhich comprises contacting said olefin at from 0* to 300*C. with acatalytic amount of the catalyst of claim
 1. 14. The process of claim 13wherein the pressure and time of polymerization are from 0 to 30,000psig. and 0.1 to 1000 minutes, respectively.
 15. The process of claim 13wherein said olefin is selected from the class consisting of ethylene,propylene, mixtures of ethylene and 1-olefins of more than two carbonatoms, mixtures of propylene and 1-olefins of more than three carbonatoms, mixtures of ethylene, 1-olefins of more than two carbon atoms anddiolefins, and mixtures of propylene, 1-olefins of more than 3 cArbonatoms and diolefins.
 16. A process for the polymerization ofethylenically unsaturated olefin which comprises contacting said olefinat from 0* to 300*C. with a catalytic amount of the catalyst of claim 3.17. A process for the polymerization of ethylenically unsaturated olefinwhich comprises contacting said olefin at from 0* to 300*C. with acatalytic amount of the catalyst of claim
 6. 18. A process for thepolymerization of ethylenically unsaturated olefin which comprisescontacting said olefin at from 0*C. to 300*C. with a catalytic amount ofthe catalyst of claim
 7. 19. A process for the polymerization ofethylenically unsaturated olefin which comprises contacting said olefinat from 0*C. to 300*C. with a catalytic amount of the catalyst of claim8.
 20. The process for the polymerization of ethylenically unsaturatedolefin which comprises contacting said olefin at from 0*C. to 300*C.with a catalytic amount of the catalyst of claim
 11. 21. The process forthe polymerization of ethylenically unsaturated olefin which comprisescontacting said olefin at from 0*C. to 300*C. with a catalytic amount ofthe catalyst of claim 12.